Process of polymerizing mono-olefines



"Patented May 14, 1935 UNITED STATES PATENT OFFICE PROCESS OF POLYMERImG MONfl-OLEFINES Samuel Lenher, gton, DeL, asslgnor to E. l. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware Application January 27, 1933,

Serial No. 653,831

l Ola.

hydrocarbon (Cullen) having less than carbon atoms.

One object or this invention is a new process tor effecting thermal treatment oi the monotill? oleflne hydrocarbons having less than 10 carbon atoms to produce higher analogs and polymers thereof. A further object comprises efiecting the pyrolysis of lower mono=oleflne hydrocarbons to yield higher mono-olefin'e hydrocmhons without the formation of excessive amounts of undesirable by-products which greatly reduce the yield of higher olefines in existing processes.

I These obiects are accomplished by the following invention in which on olefine hydrocarbon, or a mixture oi olehne hydrocarbons or olee-containing gas is heated w an elevated temperature in the presence of relatively small amounts oi oxygen.

' The process of the present invention may be carried out in the apptus described in my copending application 1m No. 533,561, filed April at, 19331. in the apparatus described in this copending application the oletlnes are pped thru an inlet tube into a reaction yessel maintained at the proper temrature, the reaction mixture being withdraw from therenotion vessel, passed in indirect relationship with the incoming gases, and thence to a condenser which may serve as a receiver, the condensed products and the spent gas being withdrawn from the condenser, the spent gas, it desired, bei recycled thru the apptus together with o ditlonal define-containing material. The reaction tube is heated by externol heating means, and further heat may be imed to the gases by heating the inlet tube.

the process is best carried out at oxygen concentrations which do not exceed 5% of the hydrocurbon concentration, the preierred oxygen concentration being below l%. it has fo found that at temperatures above tilt" C. oxygen causes not only an oxidation of oieflne hydroc oxidation products contai w oxygen, but causes in addition a decomposition, condensation, and polymerization of the ole-fine hydrocarbons to form oleilne products of higher molecular weight and also con to the formula CnHZn. Y My copending application referred to above states that olefine hydrocarbons-with art more of oxygen yield valuable oxidation products at elevated temperatures. The present invention is limited to oxygen concentrations below the range covered in the said copending application, for it has been found that only in the presence of relatively small amounts of oxygen, i. e., of 5% or less, with or without a correspondingly small amount of inert diluent gas, such as nitrogen or methane, is the condensation and polymerization of the olefines and their decomposition products efiected to any consider- 10 able degree in addition to the consumption of oxygen by the oleflne. The rate of polymerization and condensation of the olefines is greatly reduced in the gas phase by dilution with appreciable amounts of inert diluent, and it is 15 therefore desirable that diluent gas, if it is prescut during the reaction, be present in non-excessive amounts.

My experiments have shown that ethylene and propylene are polymerized to higher olefine prod- 2o nets in the presence of less than 1% of oxygen at elevated temperatures under conditions under which the oxygen-free gases are unreactive and are not polymerized. For example, under my conditions oxygen-free ethylene was not changed on heating for three seconds in glass or metal vessels at 535 (i and oxygen-free propylene was not changed on heating for 10 seconds at 510 C. Under the same conditions, using ethylene containing 0.5% to 1% of oxygen, all the oxygen was so consumed by the ethylene and in addition. an amount of ethylene equal to that used up in consuming the oxygen was polymerized to yield the products, propylene and butylen-e. Again under the same conditions propylene containing 0.5% to 1.0% of oxygen was oxidized to consume all the oxygen and in addition an amount of propylene equal to that used up in consuming the oxygen was transformed to yield the products, butylene, lens, and hexylene.

At 600""0. with ethylene in the apparatus described in my copending application already reierred to, and with oxygen prescntin an amount slightly less than 0.5% of the ethylene, three All times as much ethylene was polymerized as was oxidized. The polymerization products in the order of their abundance were propylene {59.3%

of the whole), butylene (12.2%), d amylene At 600 C. with propylene containing slightly so less than 0.5% oxygen two and one-hall times as much propylene was polymerized was oxi dized. The polymerization products in the order of their abundance were olefines above CcHn,

boiling range -l00 C. (30.4%), hexyienes 6h 5 tion, adsorption or by solution or refrigeration or (32.3%), amylenes (27.4%), and. butylenes (9.3%).

With an increase in temperature and at a heating period of less than 10 seconds, and preferably of less than 2 seconds, the amount of olefine polymerization in the presence of small amounts of oxygen increases rapidly. At a temperature of about 600 C. the polymerization takes place without separation of carbon or hydrogen or excessive formation of methane and other paraffins. At temperatures above 650 C. decomposition of the olefines and their polymerization products becomes an important reaction with a consequent lowering in the yield of the desired polymerization products.

This polymerization of the olefines in the presence of small-amounts of oxygen proceeds rapidly without explosion or inflammation in the free space of an unpacked vessel and it has been found less favorable to the reaction to use narrow tubes or packed vessels for this process. Reaction vessels which ofier little resistance to the fiow of the gas are therefore preferred.

The temperature at which this process may be carried out may vary from 400 C. to,700 C. but the preferred temperature range is between 550 C. and 650 C. At the lower temperatures the reaction products comprise mainly the next higher members of the olefine series, as with ethylene, propylene is the principal product, and. with propylene, butylene is the principal product. For example, with ethylene and with slightly less than 1% of oxygen at 490 C. and a timegof heating of three seconds the reaction product contained 91.4% propylene and 8.6% butylene, and at 600 C. the reaction product contained 59.3% propylene, 12.2% butylenes, and 28.4% amylenes. With propylene and with slightly less than 1% of oxygen at 500 C. the reaction product contained 23.4% butylenes, 23.0% amylenes, and 53.6% hexylenes, and at 600 C. the reaction product contained 9.3% butylenes, 27.4% amylenes, 32.3% hexylenes, and 30.4% higher olefines boiling from -100 C. It is evident from these examples that the nature of the pyrolytic products can be controlled by adjusting the temperature conditions.

This process may be operated as a batch process or as a continuous or flow process. It is preferred to carry out the process in a flow system or in a recirculation system in which the reaction products are separated from the reacting gases during each cycle. In the operation of a continuous process oxygen should be fed in with the hydrocarbon gases in order to maintain the oxygen concentration at a constant amount (less than The products may be separated by absorpany other of the well known means of separating the olefin hydrocarbons. from gaseous mixtures. In a continuous process using a series of reaction chambers 01' any recirculation system where the gas is passed a succession of times through the same reaction chamber, it is necessary to add oxygen to the gases as it is consumed during the run in order to maintain the formation of the hydrocarbon reaction products.

This process permits of a number of modifications, which will be "evident from the above disclosure. It is possible to operate this process at atmospheric pressure, at reduced pressure or at high pressures, but it is preferred in general to operate at atmospheric pressure or under applied pressure.

While the process has been described particularly with respect to ethylene and propylene, it is also applicable to higher olefines such as amylene, hexylenes, octylenes and nonylenes. It is, however, particularly advantageous when used with the lower olefine such as butylene and particularly with ethylene and propylene.

This process is of particular advantage because it enables the valuable higher mono-olefine hydrocarbons to be produced from the lower olefines at lower temperatures and in better yields at these temperatures than has been the practice heretofore.

The above description and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of the invention is'intended to be included within the scope of the claims.

I claim:

-1. A process of polymerizing mono-olefines to form mono-olefines of a greater molecular weight, which comprises heating a. mono-olefine having less than 10 carbon atoms under a temperature of 400-700 C. while admixed with oxygen of a con- "centration of between about 0.5% and 5% based on the olefine.

2. The process of claim 1 in which the tempera ture range is 550 to 650 C.

3. The process of claim 1 in which the oxygen content is between about 0.5% and 1%.

4. The process of claim 1 in which the reaction takes place in free space.

5. The process of claim 1 in which the gaseous mixture is passedthru a heated reaction vessel which offers no substantial resistance to the flow ofthegas. v I

6. The process of claim 1 in which the gaseous mixture is passed thru a heated reaction vessel in which the period of heating per unit of gas is less than 10 seconds. .f

'7. The process of 'claim 1 in which the gaseous mixture is passed thru a heated reaction vessel in which the period of heating per unit of gas is less than 2 seconds.

8. The process which comprises heating ethylene containing between about 0.5% and 5% oxygen at a temperature of 400-700 C.

9. The process which comprises heating propylene containing between about 0.5% and 5% oxygen at a temperature of 400-700 C.

10. In a process for forming compounds of higher molecular weight from compounds of lower molecular weight, the step which consists in heating a gaseous mixture of a mono-olefine having less than 10 carbon atoms and oxygen in the. concentration of between about 0.5% and 5% based on the olefine content, under a temperature of SAMUEL LENHER. 

